Process for decreasing ethylenic polyunsaturation in organic carboxylic acids using a co-catalyst

ABSTRACT

THIS INVENTION PROVIDES A PROCESS FOR DECREASING THE ETHYLENIC POLYUNSATURATION BY REACTING POLYUNSATURATED ALIPHATIC ACID COMPOUNDS OR DIUNSATURATED CYCLOALIPHATIC ACID COMPOUNDS IN THE PRESENCE OF IODINE DISPROPORTIONATION CATALYST AND A METAL COMPOUND ACTIVATOR.

United States Patent ABSTRACT 01* THE DISCLOSURE This invention providesa process for decreasing the ethylenic polyunsaturation by reactingpolyunsaturated aliphatic acid compounds or diunsaturated cycloaliphaticacid compounds in the presence of iodine disproportionation catalyst anda metal compound activator.

The treatment of natural resinous products, specifically thosecontaining rosin acid, and of natural and synthetic fatty acids has longbeen carried out using catalysts such as iodine, sulphur, sulfurdioxide, platinum or palladium black, selenium, nickel metal and othermaterials to obtain more useful and more stable products for use inindustry. This disproportionation treatment of the rosin acids presentin these natural resious products converted the ethylenic diunsaturatedcarboxylic acids present, such as abietic acids and its relatedstructural isomers, to mixtures of the more stable and useful saturatedacids, e.g. tetrahydroabietic acid, monounsaturated dihydroabietic acidand the aromatic dehydroabietic acids. Such disproportionation treatmentusually also results in some polymerization of the original unsaturatesto form a higher molecular weight and more stable material.

A similar process is carried out on unsaturated fatty acids, i.e.generally aliphatic acids, and other polyunsaturated aliphatic acids,such as are obtained from vegetable and animal oils. Generally thesematerials include unsaturated acids, such as oleic, linoleic acids, andarachidonic acid. Under similar conditions, including the catalyst, asare applied to the cycloaliphatic rosin acids, the fatty acids undergo asomewhat different series of reactions, including dimerization andhydrogenation of the polyunsaturates. The molecules which dimerizerelease hydrogen which is used to hydrogenate the other molecules. Thistends to increase the stability of the material. The prior art generallyfound that mixtures of rosin acids or other cycloaliphatic acids, andadiphatic unsaturated fatty acids were diltlcult to disproportionate ormodify without an undesirable chemical change in the acids which resultsin a product which did not have desirable properties.

Generally, the reaction of the aliphatic acids and the cycloaliphaticacids are slightly different. This is believed to be due to theformation of the stable aromatic acids by the dehydrogenation of thecycloaliphatic acids, e.g. abietic acid; the aliphatic diunsaturatedacids have a greater tendency to polymerize upon isomerization.

The processes for carying out such treatments, or disproportionation,are described for example, in U.S. Pats. Nos. 3,157,629 to Patrick and3,277,072 to Patrick et al., for fatty acids and rosin acidsrespectively.

The use of two different catalysts is described in British patentspecification No. 1,021,757. The patentee points out however that thesimultaneous use of two different catalysts is undesirable as it resultsin the formation of an undesirable nondecolorizable, black gum. Howeverwhen iodine and sulphur are used consecutively rather thansimultaneously, i.e., hydrodehydrogenation reactions involving abieticacid are carried out by sequentially using iodine and sulphur ascatalysts, a uniform product is 0btained regardless of the source of theresin aid feed, e.g. from wood rosin or from tall oil.

An unrelated type of treatment for rosin has involved the application oflarge amounts of metal compounds, generally in order to reduce the acidnumber value of the resin. Such treatments have used from 10% to about30% by weight of metal salt in the rosin acid and resulted in the changeof acid number in part, at least, due to decarboxylation of the resinacids at the temperatures employed. For example, see US. Pat. Nos.2,311,200 to Auer and 2,293,038 also to Auer. This latter type oftreatment, however, isnot relevant to treatments where the desiredproduct contains the greatest possible yield of dehydroabietic acid by adisproportionation reaction.

In accordance with the present invention, a process is provided forreducing the proportion of ethylenic polyunsaturation in aliphatic andcycloaliphatic carboxylic acid compounds to a greaer degree and in ashorter time than previously obtainable and without the application ofpressure. The present invention provides a process for changing thedegree of unsaturation of an aliphatic acid or a cycloaliphatic acid,without decarboxylating or otherwise degrading the material, by heatingthe polyunsaturated acids in the presence of preferably iodine, as thedisproportionation catalyst, and a metal. compound co-catalyst, oractivator.

The process of the present invention can be carried out in either anopen or closed reaction vessel and under either batch or continuousconditions. The temperature of the reaction is generally from about C.up to about 300 C. Below 175 C., although some amount of reaction canoccur, reaction rate is so slow even with the combined catalyst of thepresent invention as to be generally uneconomic. Above 300 C.,decarboxylation can occur, thus decreasing the acid quality of theproduct. The preferred temperature range is from about to about 275 C. arange within which a satisfactory reaction rate occurs without anysubstantial decarboxylation of the acid compounds.

The reaction can be carried out in a closed or open vessel becausepressure has substantially no direct effect on the present reaction.

The components of the reaction mixture, including the ethylenicallypolyunsaturated carboxylic acid compounds and other materials mixedtherewith, to be treated, the catalyst and co-catalyst are mixed in thereaction vessel; alternatively, premixing of two or more of thecomponents can occur with the final mixing occurring in the reactionvessel. For example, the activator can be premixed with either thecatalyst or with thepolyunsaturated acid. In a continuous reactionprocess, the feed and efiluent is balanced so as to maintain a constantdesired concentration of reagent and product in the reaction zone.

The present process is applicable to aliphatic polyunsaturatedcarboxylic acids and cyclo-aliphatic diunsaturated carboxylic acids andmixtures containing such acids. An advantage of the present process isthat it is applicable to both the conjugated and the nonconjugateddiunsaturated acids. The other ingredients which can be present in thereaction feed material include other acids and esters; generally anycompound which does not interfere with the present reaction can bepresent. The process is especially applicable to mixtures of acidcompounds derived from natural products, e.g. materials such as woodrosin, tall oil and gum rosins or animal-and vegetable-derived fattyacids. Generally, tall oil consists of mixtures of the aliphatic fattyacids and the primarily cycloaliphatic rosin acids. The major chemicalcomponents of rosins include abietic and pimaric acids and their variousisomers, and linoleic acid plus oleic acid. The naturally occurring fishand vegetable, or seed, oils and fats generally contain the unsaturatedfatty acids, i.e. oleic, linoleic and linolenic acids; animal-derivedoils include the polyunsaturated arachidonic acid. These natural oilsoften contain the acids in the form of esters, especially theglycerides.

The preferred acid compounds can be represented by the formula R-(COOR')the R and R groups are pref erably hydrocarbon groups or inertlysubstituted such groups. Any atom or group which does not interfere withthe reaction of the present process can be present attached to the R orR groups. It is only necessary that R have a central canbon-tocarbonstructure, straight-chain or branched chain, or alicyclic, whichcontains at least two ethylenic carbon-to-carbon unsaturated bonds, e.g.-C=CC=C-. R can be saturated or unsaturated. Any unsaturation presentcan be treated by this process in the same manner as the unsaturation inthe R group. Inert groups that can be present on the R and R groupsinclude halogen atom, ether groups and amine or amide groups. Thecarboxyl groups can be present as the free acid, i.e. where R is H, oras an ester, i.e. OOOR, wherein R is an ester group as defined above.Where a polycarboxylic acid is treated, the acid can be fully orpartially esterified.

The number of carboxyl groups, x can be any number greater than 1.Generally, acids having more than five canboxyl groups are notavailable, and not more than two carboxylic groups is preferred.

Preferably, the alicyclic R groups contain six-carbon atom ringstructures. These favor the formation of the stable aromatic structurewhen tri-unsaturation is present and thus favor the disproportionationreaction desired.

Generally, any polyunsaturated aliphatic or cycloaliphatic carboxylicacid can be treated in accordance with the present invention.Preferably, however, unsaturated carboxylic acids containing from about5 to about 36 carbon atoms, and preferably from about 8 to about 24carbon atoms, and usually monocarboxylic acids, are treated. Thecycloaliphatic acids include diunsaturated cycloaliphatic acids such asabietic acid, dextroand levopimaric acids, palustric acid, neoa bieticacid, dihydrobenzoic acid, gorlic acid, o-dihydrotoluic acid, 3,4,5-trimethoxy-dihydrobenzoic acid.

Aliphatic acids that can be treated in accordance with this inventioninclude, for example, 9,12- and 9,11-linoleic acid, linolenic acid,sorbic acid, 4methylene-2,4-pentadienoic acid, 4-pentyl 2,5heptadienedoic acid, butadiene carboxylic acid, methylsorbic acid,ethylsorbic acid; diallylacetic acid; geranic acid; 2,3,4-decadienoicacid; {3- vinylacrylic acid; 2,4-hexadienoic acid, 2,4-decadienoic acid,2,4-dodecadienoic acid, 10,13-nonadecadienoic acid, 11,14 eicosadienoicacid, 17,20 hexacosadienoic acid, hiragonic acid, zxand B-eleostearicacids, punicic acid, linolenelaidic acid, moroctic acid aand B-parinaricacid, arachidonic acid, timnodonic acid, clupanodonic acid, 6,9, 12,15-and 4,7,10,13-hexadecatetraenoic acids; 6,9,12- and4,7,10-l1exadecatrenoic acids; 9,12-, 6,9- and 7,10-hexadecadienedioicacid, diallylmalonic acid, dimethylene succinic acid, diisopropylidenesuccinic acid; and dissovaleroglutaric acid.

The esters of the above acids can be treated. Often the naturallyoccurring fatty acids are obtained as the glycerides, which can betreated directly without preliminary treatment to obtain the free acid.The materials from which the higher molecular weight diunsaturatedcycloaliphatic acids are derived include for example rosins, such astall oil rosin, gum rosin, wood rosin, copals, which include bothcontemporary and fossil gums.

The fatty acid-containing materials include, in addition to the rosinsset forth above, generally the fish or vegetable fats and oils andWaxes, such as tall oil, tung oil, linseed oil, castor oil, poppy seedoil, coconut oil, sunflower oil, rapeseed oil, walnut oil, pipe oil,corn oil, olive oil, kelp bass oil, cod liver oil, menhaden oil andsalmon oil.

When treating any mixture derived from a naturally occurring material bythe process of the present invention, it is not necessary to separatethe fatty acids from the cycloaliphatic acids in order to obtain thedesiied hydrogenation-dehydrogenation, or disproportionation, reactions.

7 The primary catalyst useful in the process of the present invention isiodine. Other catalysts which generally have the effect of initiatingand supporting disproportionation, or dehydrogenation-hydrogenation,reactions of diunsaturated cycloaliphatic acids and polyunsaturatedaliphatic acids include for example, sulphur dioxide (S0 certain of thenoble metals, particularly platinum black and palladium black, selenium,sulphur and nickel metal.

Iodine is generally present in proportions of from about .01% to about3% by weight of the unsaturated acid to be treated. Preferably at leastabout 0.1% by weight of the catalyst is present and under mostcircumstances more than about 1% by weight of the catalyst isunnecessary and does not substantially affect the course or speed of thereaction. Although more catalyst can be used, if desired, it would notprovide any substantial advantage and would thus be wasteful.

The iodine catalyst, or its reaction products, can be readily removedfrom the product by sparging with an inert gas such as carbon dioxide,nitrogen, or superheated steam, at the temperature of reaction.

The metal compound co-catalysts are referred to as activators becausethey increase the efficiency and the activity of the catalyst, but bythemselves do not have any catalytic activity in this process. Any metalcompound is useful which provides metal in an immediately soluble formto the reaction mixture.

Although metals of group 1a of the Periodic Table, i.e. the alkalimetals, are generally not useful in this process because they poison theiodine catalyst, the other metals are generally useful. Metals of groups1b, 2b, 3, 4, 5b, 6b, 7b and 8b are especially useful. Metals which havebeen found to be especially useful include, for example, iron, copper,tin, manganese, lead, aluminum and zinc. Other useful metals includeantimony, germanium, cadmium, mercury, nickel, cobalt, chromium,vanadium, titanium, zirconium calcium, tungsten and barium.

The metals can be present in any readily solubilized form. Certain ofthe more active metals can be added in finely divided elements form thatcan react quickly with the unsaturated acids, or other acid present inthe reac tion mixture, to form a soluble compound in situ. Preferably,the metal compound is soluble in both the reaction mixture and theproduct. For many purposes the small amount of metal present need not beremoved. However, if it is desired to remove it, a metal compound whichis soluble in the reaction mixture but which precipitates from theproduct is preferably used.

The metal compound can usefully be a salt, preferably of an organiccarboxylic acid. However, any metal compound can be used which containsa negative portion which will not interfere with the reaction and whichis soluble in the reaction mixture. The negative portion of the metalcompound merely serves as a solubilizer for the metal. The metal ispreferably present in amounts of from at least about 5 ppm. metalcontent, based on the total amount of feed, and usually at least 10 ppm.metal is needed. It is generally not desirable to add more than about500 ppm. metal. It is desirable to avoid any significant reactionbetween the unsaturated acids treated and the metal compounds. If toomuch metal is present, this could cause some decrease in acid number.The salt anion merely renders the salt soluble in the reaction mixture.Generally, an organic acid preferably contains at least four carbonatoms. A too high molecular weight will require an excessive amount ofthe total salt to be added to obtain the desired amount of metal contentand is therefore unnecessarily wasteful.

Accordingly, an acid containing more than 36 carbon atoms is unnecessaryand optimally the salt acid contains from about 4 to about 24 carbonatoms. Where possible, the metal salt preferably is the salt of an acidwhich is present in the reaction mixture either in the feed or as one ofthe reaction products. If the acid is a polyunsaturated centrifugationor other separating means to remove the metal oxalate precipitate.

In the following working examples where rosin acid materials areprocessed, these materials generally contain abietic acid and theeffectiveness of the reaction process acid, it would, of course, bechanged in accordance with 5 is determined at least in part by theproportion of the the hydrogenation-dehydrogenation reaction of thisprocdesired dehydroabietic product in the final product and ess.Therefore the acid can be either saturated or mono, the decrease inabietic acid compared to the feed. The di, or tri, etc. unsaturated, orcan be aromatic. Similarly, avoidance of decarboxylation is shown by thetest for acid salts of either mono or polycar boxylic acids can be used.10 value of the product.

The metal salts can be the salts of aliphatic acid such In the followingexamples, the acid value was deteras the fatty acids (saturated orunsaturated), aromatic mined by the ASTM D 465-59 method; the titratingwith carboxylic acids or cycloaliphatic carboxylic acids. Exstandard KOHsolution of a l-gram product sample. amples of such organic acidsinclude linoleic acid, abietic In the following example, the analysisfor resin acids acid, stearic acid, fumaric acid, 2-ethylhexanoic acid,was made according to ASTM method D 1585-58T lauric acid, pentadecanoicacid, cyclohexane acetic acid, (Wolff method). Alternatively theanalysis can be obbenzoic acid, maleic acid and succinic acid. Otherorganic tained by analyzing for fatty acids according to ASTM metalcompounds which are soluble in the reaction mixmethod D 1585-58T and forunsaponifiables by ASTM ture include amine salts such as irontriethanolamine. method D 1065-56 and subtracting these values fromInorganic metal compounds can al o be used. These 100% to obtain theproportion of resin acids present. The include, for example, metalhalides, such as the chlorides, latte! method y at times be moreaccurate n Vi w f iodide a d b o id the fact that the Wolff method makesthe assumption that Metals having multiple oxidation states and whichcan the resin acids have a molecular Weight equal to abietic become partof a complex negative portion of a molecule acid which is not alwaysaccurate and in certain circumare preferably present in the cationic, orpositive portion, 5 stances can result in a lower value of resin acidcontent of the molecule. than is actually the case.

Generally, the various metals do not produce the same EXAMPLESreactivity 1n the reaction process of this 1nvent1on and i d i ipossible to vary the product Obtained by To a glass-lured 1 l1terreact1on1 vessel was added 500 varying the metal salt activator present.The metals can of rosm aclds kPOWH as Q: PramiXed be used alone or incombination. This permits an addi- Yvlth Iron rfisulate co'catalyst theP P F Shown tional method to easily vary the properties or composi nTable I; 1od1ne was added 1n the proport1ons set forth tion of the finalproduct. For example by varying the 111 Table I. The materials wereheated to the temperature metal, a product having a higher or a lowermelting point shown m h table i mamtamed at a tempelamre can beobtained; ferrous or copper salts tend to provide {or the penod ShownTable The heatmg was i q the highest melting point product because theyappar t1nued;the react1on mlxture was sparged to remove 1od1ne entlyfavor the dehydroabietic acid formation. The variby superheated Ste.amthrough the mlxtur? for OHS metals can be used alone or Combination ofmetals fifteen mmutes at the react1on temperature. The mixture can beadded to obtain the desired properties in the final was then pefrmlttedto furiher c001 and was analyzed Product 40 hglprlopert1es of theobtained products are recorded in One especiall important advantage ofthe process of a e this invention is that an extremely light-coloredproduct The tau O11 rosm feed had the followmg composmon: can beobtained. This has been an especial problem with y pim ric acid 3.7 thetreating of rosin materials and the art has undertaken y pim ic a id 5.1many special treatments to obtain a disproportionated DXtYP1mafiC d 6.4resin which is as light as is obtained inherently from theDlhydroabietic acid 10.4 process of the present invention. It has beenfound that Telrahydroabietic acid 7.3 a stannous compound or a stannouscompound blended Levopimafic & Palustfic; a id 5.2 with an ironcompound, provides the lightest colored Abietic d 33.6 ProductDehydroabietic acid 213 For most purposes it is generally not necessaryto re- Neoabietic acid 1.8 move the metal activator from the product.The metal other components 5.2 is P Q in Such minute quantities thalt fdoes not intar The feed had an acid value of 174.0 and a melting pointfere w1th the use of the product. If 1t 1s desired to reof 59 C. Thecolor of the product in these and ub move a soluble metal compoundhowever, any of the quent examples was determined by visual comparisonwith conventional methods for doing so would be applicable, certifiedcolor cubes known as the US. Rosin Standard including treatment withoxalic acid followed by filtration, and French Rosin Scale, ASTM D-509055.

a TABLE I Go- Dehydracat., I Temp Time, Acid Abietic, abietic, M.P.,Examplenumber p.p.m. percent min. value percent percent C Color ControlA0 0.3 225 5 170.5 12.1 38.0 43.0 4A 1 a 10 0.3 225 5 173.5 4.5 43.6 49.05A 30 0.3 225 5 171.8 0.0 43.5 46.0 5A 0 0.3 225 15 172.0 14.0 37.6 50.04A 10 0.3 225 15 169.0 1.0 53.2 47.0 5A 30 0.3 225 15 170.6 0.0 50.543.0 5A 0 0.3 275 5 165.0 7.2 35.9 35.0 4A 10 0.3 275 5 166.5 2.3 35.231.0 5. 30 0.3 275 5 169.5 0.0 46.8 47.0 5A 0 0.3 275 15 166.3 2.1 35.830.0 411 10 0.3 275 15 153.7 0.0 41.2 31.0 5A 30 0.3 275 15 167.5 0.046.1 46.0 44

As shown from the above test data, the acid value of the feed issubstantially unchanged in the product. The

iodine and metal co-catalyst present, the temperature of the reactionand the reaction time.

TABLE II Dehydro- Amount Wt. Acti- Temperabietic abietic Example percentvator, ature, Time Acid M.P., acid, wt. acid, wt. number catalystActivator ppm. C min. value 0. percent Color percent 0.5 Aluminumresinate. 100 235 75 2 0.3 Zinc resinate 200 250 180 0.5 Iron resinate.50 235 60 o 12 0.3 .do 150 235 30 0 Control F 0. 00 235 288 o abieticacid content however is decreased in all cases compared to theComparative Examples A through D, which I did not contain the salt, anddecreased to substantially The meltmg pomts In and succeedlns e pl zeroin most cases. The dehydroabietic acid content is Were tam d by theconventlonal capillary melting point also substantially increased as aresult of the addition of testthe metal co-catalyst as shown, thereaction time needed EX MPLES 13 THROUGH 22 to obtain substantially zeroabietic acid is no more than five minutes in many cases. This should becompared with The Process of E P 1 was rePe ated but t fi' the reactiontime of an hour and a half or longer required E f the tall 011 @5111used therem tall 011 by the prior art to completely disproportionate allof the identified as SP-14, WhlCh had the following composition: abletlcacld: utlhzlng lodlne alone- Tetrahydrodoxtropimaric acid EXAMPLES 9 THRH 12 Dihydroisodextropimaric acid The process of Example 1 was repeatedbut substituting f f l aclfi Telogia Wood rosin for the Tall oil rosin.The Telogia Dlhydroabletlf: a Wood rosin had the following composition:Tetraltydrqablem r":

Levop1mar1c & Palustric acid 4.0 Ac1d$1 Abietic acid 32.1 Plmal'lcDehydroabietic acid 23.0 e yq pg o Neoabietic acid 1.8Dlhydro'lsode'xtroplmarlc Other components 5.0 Dextropimaric 0.7Dihydroabietic 1.4 The product was evaluated as above and the data isTetralrrydroabietic 2.7 set forth in Table III together with thereaction conditions Levopnnaric & Palustrlc 7.3 and proportions ofcatalyst and activator. Comparing Abtetrc 42.6 Control F, whichcontained no metal salt, with the ex- Dehyd roabietlc 9.8 amples of thisinvention, shows the increase in dehydro- Neoabietic 6.2 abietic acidcontent obtained. Isopimaric 16.4 Other components 5.8

TABLE III Dehydro- Amount Wt. Acti- Temperabietic abietic percent.vator, ature, Time Acid M.P., acid, wt. acid, wt. catalyst Activatorp.p.m. 0. min. value 0. percent Color percent 0.3 Iron amine salt 100235 15 46.8 WW 0 0.15 Iron resinate 235 20 51 4A 0 0.3 do 25 300 3 44.63.4 0 0.3 do 25 235 15 43.5 6A 0 0.3 Iron fumarate 30 235 10 45.7 4A. 00.3 Lead tallate 235 30 45.0 4A 0 0.3 Tin resinat 100 250 15 44.0 5A 00.3 do 100 235 30 54.4 7A 0 0.3 $1no1lea 2 235 15 50.4 5A. 0

0 8- {lrh r i rgs inate 30 235 20 a 0 Control F 0 3 235 50 35 2A 0 aSoft.

The products obtained were tested and the results set EXAMPLES 23THROUGH 29 The process of Example 1 was repeated but using the forth inTable 11 below together with the proportions of 60 same tall oil rosinacid mixture. The reaction conditions,

catalysts and the results of tests on the product are set forth in TableIV.

TABLE IV V V v v o Dehydro- Amount Wt. Acti- Temperabietic abieticExample percent vator, ature, Time Acid M.P., acid, wt. acid, wt. numbercatalyst Activator p.p.m. 0. min. value C. percent Color percent 03 Ironresinate 25 235 15 171.5 51.5 50.2 7A 0 0.3 do 25 275 15 164 48 54 3A 00.3 Iron oleate 25 275 15 166.4 52 2A 0 0.3 Cooperresinate 10 275 15161.5 Soft 32.9 3A 0 0.3 Manganese resinate. 25 275 15 169 Soft .1-..4A. 0

Fe stearate 50 0.3 plus 225 30 170; 53.6 2A 0 A1 reslnate 50 29 0.3 FeCl225 50. 4A 0 Control G 0.3 235 36.6 2A 0 0.3 275 35.3 4.0

V 3 Rosin distilled prior to disproportionation.

9 EXAMPLES 30 THROUGH 32 The procedure of Example 1 was repeated butsubstituting for the tall oil rosin used therein a Portuguese gum havingthe following composition:

The reaction conditions and composition and proper- TABLE VII Tempera-Example number Acid ture, C.

35 Dimethylene succinic acid 210 36 B-Vinyl acrylic acid 200 37- Sorbicacid 200 38- Arachidonic acid.-- 235 39- Diallylmalonic acid 280 40.7,10-hexadienedioic aci 235 41-.- 4,7,10,IB-hexadeeatetraenorc acid 23542 Ethylsorbic acid 200 In each example there is a substantial decreasein the degree of unsaturation in the product compared to the acidtreated.

EXAMPLE 43 The process of Example 1 is repeated but substituting ties ofthe product resulting from this process are set the acids shown, andcarrying out the reactions at the forth in Table V. temperature shown,in Table VIII.

TABLE v Dehydraabietic Wt. Acti- Temperacid, Example percent vator,ature, Time, Acid M.P., wt. number catalyst Activator p.p.m. C. min.value 0. percent Color 0.5 Iron resinate 30 200 120 160 57 37.2 x 0.3Iron iumarate.-. 30 235 30 162 43.5 x 0.3 Iron resinate 30 235 60 161 4341.6 2A 235 120 160 Soft 2:

EXAMPLE 33 TABLE VIII The process of Example 1 was repeated but sub-Temperastituting for the tall oil resin used therein a Mexican gumExample number ture having the composition: 43 Dihydrobenzoie acid 23544 o-Dihydrotoluic acid 250 Prmarrc acid 8.5 Dextropimaric acid 18 8Dihydroabietic acid In both of the above examples there is a substantialTetrahydroabietic acid 2.0 21:15am of bcnzolc acid and toluic acidformed, respec- & Palusmc acld With reference to the above descriptionthe patentable Deh g 'z' z embodiments of the present invention are asfollows:

y a 1. A process for decreasing the ethylenic unsaturation Othercomponents 10.8

The process conditions of the reaction and the data on the final productare set forth in Table VI below.

of a polyunsaturated aliphatic carboxylic acid or a dimsaturatedcycloaliphatic carboxylic acid without decarboxylating or otherwisedegnading the material, the proc- TABLE VI Dehydraabietic Wt. Acti-Temperacid, Example percent vator, ature Time, Acid M.P., wt. numbercatalyst Activator p.p.m. 0 min. value 0. percent Color 33 0. 3 Ironresinate 30 235 30 150 48 WW Control I .7 230 120 155 Soft 30 WW EXAMPLE34 A castor oil derived linoleic acid composition (Baker- 911 SA), whichcontained wt. percent linoleic acid was treated.

The above linoleic acid composition was mixed with 100 p.p.m. ironstearate in an open glass-lined vessel and mixed With 0.3% iodine andheated to 235 C. The mixture was maintained at 235 C. for approximately60 minutes at which time heating was discontinued and the material wassparged with carbon dioxide for approximately 15 minutes to remove theiodine.

The product was analyzed and found to contain only a trace of linoleicacid and showed a substantial increase of oleic type acids to about 81%.

EXAMPLES 35-42 Example 34 is repeated but substituting the followingacids for the Baker-911 SA and carrying out the process at thetemperature indicated in Table VII.

ess comprising dispersing into such ethylenically polyunsaturatedaliphatic acid compound or ethylenically dinnsaturated cycloaliphaticacid compound, to be treated, iodine disproportionation catalyst and anactivator comprising at least one metal compound soluble in the acid,the metal being nonpoisonous to the iodine catalyst, and heating theacid compound.

2. The process of claim 1 wherein the metal compound is the salt of anorganic carboxylic acid.

3. The process of claim 1 wherein after heating is discontinued, theiodine is removed by sparging with a gas inert to the reactants of thisprocess.

4. The process of claim 3 wherein the inert gas is super heated steam.

5. The process of claim 1 wherein the iodine is present in an amount offrom about 0.01 to about 3 percent by wt. of the unsaturated acidcompound being treated.

6. The process of claim 1 wherein the metal compound is present in anamount of from about 5 to about 500 p.p.m. by wt. of metal of totalmaterial present.

7. The process of claim 1 wherein the metal compound is a salt of ametalselected from the group consisting or barium calcium and the metals ofgroups 1b, 2b, 3, 4, 5b, 6b and8b Qft q P o Tab e 8. The process ofclaim 1 wherein the metal compound is a salt of a metal selected fromthe group consisting of iron, copper, tin,'zinc, aluminum, lead andmanganese. 9. The process of claim 8 wherein the metal is tin.

10. The process of claim 8 wherein the metal is iron.

11. The process of claim 1 wherein the reaction mixturei's heated to atemperature in the range of from about 175 to about 300 C.

'12. The process of claim 1 wherein the unsaturated acid compound to betreated has the formula R(COOR) wherein R is a polyunsaturated aliphaticgroup or a dinnsaturated cycloaliphatic group, R is hydrogen, R or aninert organic group and x is an integer equal to at least one.

13. The process of claim-12 wherein R is a hydrocarbon group containingat least two ethylenically unsaturated carbon-to-carbon linkages andcontaining fro about 5 to about 36 carbon atoms. I Y

14. The process of claim 13 wherein R is hydrogen.

15. The process of claim 14 wherein x is a number from one to aboutfour.

16. The process of claim 1 wherein the metal salt is the salt of ahydrocarbyl carboxylic acid wherein the hydrocarbyl group is selectedfrom the group consisting of aliphatic, cycloaliphatic and aromaticgroups.

17. The process of claim 16 wherein the metal salt is the salt of anacid being treated.

18. The process of claim 1, wherein'the unsaturated acid compound to betreated is a rosin acid.

19. The process of claim 18 wherein the acid compound to be treatedcomprises abietic acid.

20. The process of claim 1, wherein the ethylenically polyunsaturatedaliphatic, acid compound to be treated comprises a fish oil. or avegetable oil.

21. ,The process of claim 1, wherein the ethylenically polyunsaturatedaliphatic acid compound to be treated comprises linoleic acid. 1

References Cited UNITED STATES PATENTS 2,503,268

DONALD E. CZAJA, Primary Examiner r W. E. PARKER, Assistant Examiner

